CN105492383A - Production device for carbon nanotubes and supply unit to become one part of said production device, and production method for carbon nanotubes - Google Patents
Production device for carbon nanotubes and supply unit to become one part of said production device, and production method for carbon nanotubes Download PDFInfo
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- CN105492383A CN105492383A CN201480046650.8A CN201480046650A CN105492383A CN 105492383 A CN105492383 A CN 105492383A CN 201480046650 A CN201480046650 A CN 201480046650A CN 105492383 A CN105492383 A CN 105492383A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
Abstract
As a means for increasing the yield of carbon nanotubes produced by gas-phase catalysis, provided is a production device for producing carbon nanotubes by gas-phase catalysis, the production device characterized by being provided with: a first chamber that has a growth region that is a region where carbon nanotubes are formed; a first temperature adjustment device that can adjust the temperature of the growth region inside the first chamber; a pressure adjustment device that can adjust the pressure inside the first chamber; a first supply device that can supply a carbon source to the growth region inside the first chamber; a second temperature adjustment device that can adjust the temperature of a solid-phase iron-group-element-containing material that is disposed inside the production device; and a second supply device that can supply a halogen-containing substance to the inside of the production device such that the iron-group-element-containing material that is adjusted to a prescribed temperature by the second temperature adjustment device can react with a gas-phase halogen-containing substance.
Description
Technical field
The manufacturing installation that the present invention relates to a kind of carbon nanotube (Carbonnanotube, CNT) and the feed unit of a part becoming this manufacturing installation and the manufacture method of carbon nanotube.
In this specification sheets, so-called carbon nano pipe array (also referred to as " CNT array " in this specification sheets), for the composite structure of many carbon nanotubes (also referred to as " CNT " in this specification sheets) is (following, the CNT shape separately forming this composite structure is called " primary structure ", by described composite structure also referred to as " secondary structure ") one, and refer to that many CNT are with the aggregate of the CNT grown up towards the mode of certain orientation (a concrete example can enumerate the almost parallel direction of the normal in the face possessed with substrate) orientation at least partially of long axis direction.In addition, will be called with the length (highly) in the direction of the normal parallel of substrate under the state being attached on substrate of the CNT array of growing up from substrate " height of growing up ".
In addition, in this specification sheets, the structure with the structure that many CNT entwine each other formed in the following manner is called " CNT entwine body ": a part of CNT pinching CNT array, by this CNT to stretch away from the mode of CNT array, many CNT (in this specification sheets, imitate and manufacture the operation of silk by fiber in prior art and operate this also referred to as " weaving ") are extracted thus continuously out from CNT array.
Background technology
CNT has following specificity structure, that is, have the outer side comprising Graphene (graphene), therefore expects to it can be used as functional materials to be also applied to as structured material in various field.Specifically, CNT has following excellent specific property: physical strength is high, lightweight, and conductive characteristic is good, and the thermal property such as thermotolerance, thermal conductivity is good, and chemical erosion resistance is high, and Field Electron Emission characteristic is good.Therefore, about the purposes of CNT, light weight high intensity line (wire), Scanning Probe Microscopy (ScanningProbeMicroscope can be expected, SPM) probe, Field Emission Display (FieldEmissiondisplay, the electrode of cold cathode FED), electroconductive resin, high-intensity resin, corrosion-resistant resin, wearability resin, high lubrication resin, secondary cell or fuel cell, the interlayer wiring material of large-scale integrated circuit (LargeScaleIntegration, LSI), biosensor (biosensor) etc.
As one of the manufacture method of CNT, Patent Document 1 discloses following methods: the film etc. of evaporation metal based material, the methods such as sputter are utilized to form the metal catalyst layer of solid phase in advance on a surface of a substrate, the substrate of the metal catalyst layer possessing this solid phase is configured in Reaktionsofen, on substrate, be formed into the catalyst particle of growth core by this metal catalyst layer, CNT array is formed on substrate to Reaktionsofen supply appropriate hydrocarbon gas.Below, as described, the catalyst particle of the solid phase as growth core will be formed on substrate, and to be provided with the catalyst particle possessing this solid phase substrate Reaktionsofen in supply the material of hydrocarbon system and the method manufacturing CNT array is called solid catalysis method.
As by solid catalysis method with the method for high efficient production CNT array, Patent Document 2 discloses following methods: one side meets the supply of established condition one side containing carbon and oxygen-free unstripped gas, catalyst activation material containing aerobic, environmental gas make the catalyst layer contacts of itself and solid phase.
Also disclose and utilize with described method diverse ways to manufacture the method for CNT array.That is, Patent Document 3 discloses following methods: iron(ic) chloride is distilled, it can be used as precursor and on substrate, be formed into the catalyzer of growth core, using this catalyzer to form CNT array.The method using containing halogen and the material being in gas phase state as catalyst precursors, use this material to form catalyzer, from this respect, different from technological essence disclosed in patent documentation 1 or patent documentation 2.In this specification sheets, by the manufacture method of CNT array disclosed in patent documentation 3 also referred to as gas-phase catalysis.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2004-107196 publication
Patent documentation 2: Japanese Patent No. 4803687 publication
Patent documentation 3: Japanese Patent Laid-Open 2009-196873 publication
Summary of the invention
[inventing problem to be solved]
Utilize in the manufacture method of CNT array of this gas-phase catalysis, the formation process of catalyzer is different from the manufacture method of the CNT array utilizing described solid catalysis method, and therefore the effect of possibility catalyzer is different.So, can think that solid catalysis method and gas-phase catalysis are the manufacture method of CNT arrays different in essence.Therefore, when manufactured by gas-phase catalysis have various primary structure, secondary structure CNT, because its manufacture method is gas-phase catalysis, therefore can provide various raising productive method.
Problem of the present invention is to provide a kind of means improving production control by the CNT manufactured by described gas-phase catalysis.
[technique means of dealing with problems]
The present invention provided to solve described problem is as described below.
[1] manufacturing installation, manufactures carbon nanotube by gas-phase catalysis, and the feature of described manufacturing installation is to possess: the first chamber, has the growth region as the region forming carbon nanotube; First register, the temperature in the described growth region in the first chamber described in adjustable; Regulator, the pressure in the first chamber described in adjustable; First feedway, can to the described growth region supply carbon source in described first chamber; Second register, adjustable is configured in the temperature containing iron group element material of the solid phase in described manufacturing installation; And second feedway, halogen-containing material can be supplied in described manufacturing installation, with make through described second register be adjusted to described in determined temperature containing iron group element material can with the described halogen-containing substance reaction of gas phase.
[2] manufacturing installation according to described [1], is wherein configured with substrate in described growth region, can form carbon nanotube on the basal plane of this substrate with array-like.
[3] manufacturing installation according to described [1], wherein in described growth region, forms carbon nanotube by gas phase flowing reactive.
[4] manufacturing installation according to any one of described [1] to [3], possess and can accommodate described iron content race element material and its inner second chamber be communicated with the inside of described first chamber, and described halogen-containing material can be supplied in described second chamber by described second feedway.
[5] manufacturing installation according to any one of described [1] to [3], possess the second chamber can accommodating described iron content race element material and the 3rd feedway that the gaseous substance be present in described second chamber can be supplied in described first chamber, and described halogen-containing material can be supplied in described second chamber by described second feedway.
[6] manufacturing installation according to any one of described [1] to [3], is wherein configured in described in described first chamber containing iron group element material.
[7] a kind of feed unit, it is the feed unit of gas phase catalyst, become a part for the manufacturing installation being manufactured carbon nanotube by gas-phase catalysis, and the feature of described feed unit is to possess: feed unit chamber, that can accommodate solid phase contains iron group element material; Feed unit register, containing the temperature of iron group element material described in feed unit chamber described in adjustable; Halogen-containing material feeding device, can be supplied in described feed unit chamber by halogen-containing material; And releasing device, the described gas phase catalyst be present in described feed unit chamber can be released to outside described feed unit chamber.
[8] manufacture method for carbon nanotube, uses the feed unit according to described [7], and the basal plane of substrate obtains the carbon nanotube formed with array-like.
[9] manufacture method for carbon nanotube, uses the feed unit according to described [7], obtains carbon nanotube with the form of the product of gas phase flowing reactive.
[10] a kind of manufacture method, it is the manufacture method of carbon nanotube, and the feature of described manufacture method is to possess: the first operation, the gas phase catalyst containing the material making the halogen-containing substance reaction gained containing iron group element material and gas phase of solid phase is supplied in the first chamber; And second operation, use the catalyzer generated based on the gas phase catalyst existed in described first chamber, by the carbon source be supplied in described first chamber to form carbon nanotube.
[11] manufacture method according to described [10], wherein in described first operation, make the substrate be configured in described first chamber be present in the environment containing described gas phase catalyst, in described second operation, the basal plane of described substrate forms carbon nanotube with array-like.
[12] manufacture method according to described [11], wherein under the state that described gas phase catalyst is present in the first chamber through described first operation, is supplied to described carbon source in described first chamber.
[13] manufacture method according to described [11] or [12], the temperature of the described substrate in wherein said first operation is lower than the temperature of the described substrate in described second operation.
[14] manufacture method according to described [10], wherein forms carbon nanotube with the form of the product of gas phase flowing reactive.
[15] manufacture method according to any one of described [10] to [14], the wherein said iron family element ting contained contained by iron group element material comprises iron.
[16] manufacture method according to any one of described [10] to [15], wherein in described first operation, outside described first chamber, carry out the reaction obtaining described gas phase catalyst, described gas phase catalyst is supplied in described first chamber from described first chamber.
[effect of invention]
According to the manufacture method of CNT of the present invention, easily in the first chamber, supply gas phase catalyst.Therefore, expecting when manufacturing CNT by gas-phase catalysis, easily controlling the characteristic of its output or its shape (primary structure and secondary structure both).
Accompanying drawing explanation
Fig. 1 is the figure of the formation of the manufacturing installation of the CNT array diagrammatically representing the first example of the present invention.
The figure of the formation of gas phase catalysis agent feeding device of Fig. 2 for diagrammatically representing the manufacturing installation shown in Fig. 1 and possessing.
Fig. 3 is the figure of the formation of an example of the manufacturing installation of the CNT array diagrammatically representing the second example of the present invention.
Fig. 4 is the figure of the formation of another example of the manufacturing installation of the CNT array diagrammatically representing the second example of the present invention.
Fig. 5 is the image representing the CNT forming CNT array.
Fig. 6 is the chart of the external diameter distribution representing the CNT forming CNT array.
Fig. 7 represents that the weaving of CNT array being manufactured CNT entwines the image of state of body.
Fig. 8 is a part of enlarged image of body of being entwined by the CNT by CNT array gained.
The observation image of the CNT net of Fig. 9 manufactured by the manufacture method by embodiment 1.
The observation image of the CNT net of Figure 10 manufactured by the manufacture method by embodiment 2.
Figure 11 is for making to be ruptured with the face comprising the direction parallel with its growth direction by the CNT array manufactured by the manufacture method of embodiment 3 and the image observed.
Figure 12 is for making to be ruptured with the face comprising the direction parallel with its growth direction by the CNT array manufactured by the manufacture method of embodiment 4 and the image observed.
Figure 13 is for making to be ruptured with the face comprising the direction parallel with its growth direction by the CNT array manufactured by the manufacture method of embodiment 5 and the image observed.
The observation image of the CNT net of Figure 14 manufactured by the manufacture method by embodiment 6.
Figure 15 is for making to be ruptured with the face comprising the direction parallel with its growth direction by the CNT array manufactured by the manufacture method of embodiment 16 and the image observed.
Embodiment
Below, example of the present invention is illustrated.
The manufacturing installation of 1.CNT array
One side with reference to graphic one in the face of the manufacturing installation of CNT array of the first example of the present invention is illustrated.
Fig. 1 is the figure of the formation diagrammatically representing the manufacturing installation used in the manufacture method of the CNT array of the first example of the present invention.
As shown in FIG. 1, the manufacturing installation 10 of CNT array possesses electric furnace 12.This electric furnace 12 presents the substantially cylindrical shape extended along set direction A (direction of unstripped gas flowing).Reaction vessel pipe 14 is through in the inner side of electric furnace 12, and described reaction vessel pipe 14 is for having first chamber in the growth region as the region forming CNT.Reaction vessel pipe 14 such as comprising the component of the general cylindrical shape of the heat-stable materials such as quartz, having the external diameter thinner compared with electric furnace 12, and extending along set direction A.In Fig. 1, in the growth region of reaction vessel pipe 14, be configured with substrate 28, this substrate 28 possesses the basal plane in the face of growing up as CNT array.That is, the growth region in the manufacturing installation 10 of CNT array comprises the region being configured with substrate 28 in reaction vessel pipe 14.
Electric furnace 12 possesses well heater 16 and thermopair 18.In the manufacturing installation 10 of CNT array, the first register is made up of well heater 16 and thermopair 18.Well heater 16 be certain certain area of the set direction A surrounding reaction vessel pipe 14 (in other words, for the axial certain area of the reaction vessel pipe 14 of substantially cylindrical shape, hereinafter also referred to " heating region ") mode arrange, produce be used for the heating region making reaction vessel pipe 14 pipe environment temperature rise heat.Thermopair 18 is configured near the heating region of reaction vessel pipe 14 in the inner side of electric furnace 12, the electrical signal of the exportable expression temperature relevant with the temperature of the pipe environment of the heating region of reaction vessel pipe 14.Well heater 16 and thermopair 18 are electrically connected with control device 20.
At the upstream side (being the one end in left side in Fig. 1) of the reaction vessel pipe 14 of set direction A, be connected to feedway 22.Feedway 22 possesses material gas supply device 30, gas phase catalysis agent feeding device 31, gas phase catalysis auxiliary agent feedway 32 and assist gas feedway 33.Feedway 22 is electrically connected with control device 20, and each feedway that feedway 22 possesses all is electrically connected.
Material gas supply device 30 (the first feedway) can become carbon compound hydrocarbon such as () such as acetylene of the raw material of the CNT forming CNT array, the unstripped gas namely containing carbon source to the inside of reaction vessel pipe 14 (region of particularly growing up) supply.Supply flow rate from the unstripped gas of material gas supply device 30 can adjust by the well-known flow regulation mechanism such as functional quality stream (massflow).
Gas phase catalysis agent feeding device 31 can supply gas phase catalyst to the inside of reaction vessel pipe 14 (region of particularly growing up).In this specification sheets so-called " gas phase catalyst ", be use with the general name of following material, described material is catalyst precursors containing halogen and the material that can obtain gas phase state in the growth region of reaction vessel pipe 14 and the suspended solid formed based on this catalyst precursors containing halogen.Form gas phase catalyst material in, be attached on the basal plane of substrate 28 at least partially, based on the material that this is accompanying, be formed help CNT array formed catalyzer at least partially.
As shown in FIG. 2, gas phase catalysis agent feeding device 31 has the following modular construction that will illustrate.That is, gas phase catalysis agent feeding device 31 possesses the feed unit register containing the temperature containing iron group element material M in the feed unit chamber 31A of iron group element material M and adjustable feed unit chamber 31A can accommodating solid phase therein.In the manufacturing installation 10 of CNT array, the second register is made up of feed unit register.In Fig. 2, feed unit register is made up of well heater 31B and not shown thermopair equitemperature measuring apparatus.The temperature containing iron group element material M of feed unit in register adjustable feed unit chamber 31A.
Gas phase catalysis agent feeding device 31 possesses the halogen-containing material feeding device 31C (the second feedway) that can supply halogen-containing material in feed unit chamber 31A.At feed unit with in chamber 31A, through feed unit register (comprising well heater 31B etc.) be adjusted to determined temperature containing iron group element material M can with the halogen-containing substance reaction supplied by halogen-containing material feeding device 31C and generate the one of gas phase catalyst.Gas phase catalysis agent feeding device 31 possesses releasing device 31D, and this releasing device 31D can contain the gas phase catalyst formed by described reaction and the gaseous substance be present in feed unit chamber 31A is released to outside feed unit chamber 31A.In Fig. 1, it disengages the inside that point of destination is reaction vessel pipe 14, is supplied in reaction vessel pipe 14 (region of particularly growing up) by the gaseous substance containing gas phase catalyst from gas phase catalysis agent feeding device 31.Halogen-containing material feeding device 31C and releasing device 31D also can possess the mechanism adjusted the amount of substance by these each devices.
The solid phase of accommodating in feed unit chamber 31A containing the concrete shape containing iron group element material M in the concrete holding method of iron group element material M or feed unit chamber 31A and indefinite.If be described for the situation being ferrous material containing iron group element material M, then can be block iron component containing iron group element material M, also can be flat iron component.Or, also can have the shape that Steel Wool (steelwool) is such, also can have netted shape.And then, also can have the shape of powder.
Gas phase catalysis agent feeding device 31 can have the exhaust system (regulator) of the pressure in adjustable feed unit chamber 31A, also can have the gas supply system (gas supply device) of the environment (concrete example can be enumerated and rinse inside with rare gas element or hydrogen) in adjustable feed unit chamber 31A.By having this exhaust system or gas supply system, the reaction containing iron group element material M and halogen-containing material more stably can be carried out.
Gas phase catalysis auxiliary agent feedway 32 can supply gas phase catalysis auxiliary agent to the inside of reaction vessel pipe 14 (region of particularly growing up).Will be described below about gas phase catalysis auxiliary agent.Supply flow rate from the gas phase catalysis auxiliary agent of gas phase catalysis auxiliary agent feedway 32 can adjust by the well-known flow regulation mechanism such as functional quality stream.
Assist gas feedway 33 can supply the rare gas elementes (being generically and collectively referred to as " assist gas " by this gas in this specification sheets) such as gas, such as argon gas beyond described unstripped gas, gas phase catalyst and gas phase catalysis auxiliary agent to the inside of reaction vessel pipe 14 (region of particularly growing up).Supply flow rate from the assist gas of assist gas feedway 33 can adjust by the well-known flow regulation mechanism such as functional quality stream.
At the other end in the downstream side (being right side in Fig. 1) of the reaction vessel pipe 14 of set direction A, be connected to relief valve 23 (part for regulator) and gas barrier 24 (being all a part for regulator).The pressure that relief valve 23 adjusts in reaction vessel pipe 14 by making the opening and closing degree of valve change.Vacuum exhaust is carried out in the inside of gas barrier 24 pairs of reaction vessel pipes 14.The concrete kind of gas barrier 24 is not particularly limited, the rotor pump that can be used alone (rotarypump), oil diffusion pump, mechanical booster (mechanicalbooster), turbomolecular pump (turbo-molecularpump), refrigerating water pump (cryopump) etc. or combinationally used by these devices.Relief valve 23 and gas barrier 24 are electrically connected with control device 20.In addition, in the inside of reaction vessel pipe 14, be provided with the pressure warning unit 13 for measuring its internal pressure.Pressure warning unit 13 is electrically connected with control device 20, can export the electrical signal of the internal pressure representing reaction vessel pipe 14 to control device 20.
As described above, control device 20 is electrically connected with well heater 16, thermopair 18, feedway 22, pressure warning unit 13, relief valve 23 and gas barrier 24, input the electrical signal exported by these devices etc., and control the action of these devices etc. based on the electrical signal that this inputs.Below, the concrete action of control device 20 is illustrated.
Control device 20 can input the electrical signal relevant with the internal temperature of reaction vessel pipe 14 exported by thermopair 18, and well heater 16 is exported to the control signal relevant with the action of well heater 16 determined based on this electrical signal.The well heater 16 that have input the control signal of self-control device carries out the action that generation heat is increased and decreased based on this control signal, the internal temperature of the heating region of reaction vessel pipe 14 is changed.
Control device 20 can input the electrical signal relevant with the internal pressure of the heating region of reaction vessel pipe 14 exported by pressure warning unit 13, and exports the control signal relevant with relief valve 23 and gas barrier 24 action that be that determine based on this electrical signal to relief valve 23 and gas barrier 24.The relief valve 23 and the gas barrier 24 that have input the control signal of self-control device 20 carry out changing the action such as the opening and closing degree of relief valve 23 or the exhaust capacity of change gas barrier 24 based on this control signal.
Control device 20 can to export each device according to the timetable preset (timetable) be used for the control signal of the action controlling each device etc.Such as, can export following control signal to feedway 22, this control signal determines the beginning of the material supply that the material gas supply device 30, gas phase catalysis agent feeding device 31, gas phase catalysis auxiliary agent feedway 32 and the assist gas feedway 33 that possess from feedway 22 are respective and stopping and supply flow rate.The feedway 22 that have input this control signal makes each feedway action according to this control signal, to start in reaction vessel pipe 14 each materials such as base feed gas or stops supply.
Control device 20 can control the action in each portion forming gas phase catalysis agent feeding device 31.That is, control device 20 can export the control signal relevant with the action of well heater 31B based on the electrical signal of the thermopair equitemperature measuring apparatus possessed from gas phase catalysis agent feeding device 31.The well heater 31B that have input this control signal makes the temperature variation containing iron group element material M in feed unit chamber 31A according to this control signal.The control signal that the action of the exportable and halogen-containing material feeding device 31C of control device 20 is relevant.The halogen-containing material feeding device 31C that have input this control signal makes the feed rate to the halogen-containing material in feed unit chamber 31A change according to this control signal.The level of response containing iron group element material M and halogen-containing material is made to change by the change of this feed rate, the output etc. of adjustable gas phase catalyst thus.The exportable control signal relevant with the action of releasing device 31D of control device 20.The gas phase catalyst generated by the reaction containing iron group element material M and halogen-containing material can be supplied to the opportunity (timing) of feed unit chamber 31A outer (that is, the reaction vessel 14 of Fig. 1 is interior) according to the adjustment of this control signal or measure by the releasing device 31D that have input this control signal.When gas phase catalysis agent feeding device 31 possesses additional exhaust system or gas supply system as described above, the exportable control signal relevant with the action of these systems of control device 20.
One side with reference to graphic one in the face of the manufacturing installation of CNT array of the second example of the present invention is illustrated.Fig. 3 is the figure of the formation diagrammatically representing the manufacturing installation used in the manufacture method of the CNT array of the second example of the present invention.As shown in FIG. 3, if the manufacturing installation 50 of the CNT array of the second example of the present invention is compared with the manufacturing installation 10 of the CNT array of the first example of the present invention shown in Fig. 1, then feedway 22 possesses the halogen feedway 51 that can supply halogen-containing material and replaces gas phase catalysis agent feeding device 31, and can will be configured in reaction vessel pipe 14 containing iron group element material M, in addition, basic comprising is identical.
In the manufacturing installation 50 of the CNT array of second example of the present invention of this formation, carry out in reaction vessel pipe 14 from halogen feedway 51 be supplied to halogen-containing material near containing iron group element material M, with the reaction containing iron group element material M.Growth region is arrived at reaction vessel pipe 14 internal diffusion by the gas phase catalyst of this reaction gained.In Fig. 3, well heater 16 adjustable is configured in the temperature of the substrate 28 in reaction vessel pipe 14, and adjustable is containing the temperature of iron group element material M.
When carrying out halogen-containing material and the reaction containing iron group element material M the manufacturing installation 50 of the CNT array as the second example of the present invention in reaction vessel pipe 14, the envrionment temperature in reaction vessel pipe 14 also can be set as divisible control in reaction vessel pipe 14.Such as, the manufacturing installation 60 of the CNT array shown in Fig. 4 possesses multiple thermopair 18A, thermopair 18B, and well heater 16 can segmentation control (upstream side, downstream side) on the direction of principal axis of reaction vessel pipe 14 based on the electrical signal from each thermopair.
Therefore, in the region of the upstream side (being left side in Fig. 4) of reaction vessel pipe 14, make the upstream side of well heater 16 (being left side in Fig. 4) action based on the electrical signal from thermopair 18A, adjustable is configured in the temperature containing iron group element material M of the part in the downstream side (being right side in Fig. 4) of halogen feedway 51 thus.In addition, the manufacturing installation 60 of the CNT array shown in Fig. 4 possesses the tubular member 61 of end of downstream side through opening in the downstream side of halogen feedway 51, be configured with containing iron group element material M in the hollow bulb of this tubular member.By having this structure, to improve and preferred from halogen the feedway 51 halogen-containing material supplied and the possibility of react containing iron group element material M.
In the region in the downstream side (being right side in Fig. 4) of reaction vessel pipe 14, make the downstream side of well heater 16 (being right side in Fig. 4) action based on the electrical signal from thermopair 18B, adjustable is configured with the temperature in the growth region of substrate 28 thus.When this formation, gas phase catalyst can be generated at the upstream side of reaction vessel pipe 14, and can in the temperature of the downstream side of reaction vessel pipe 14 adjustment conversion zone.
The manufacturing installation of the CNT array of an example of the present invention also can possess the multiple structural feature of the manufacturing installation 10 of described CNT array, manufacturing installation 50, manufacturing installation 60.Namely, also CNT device can be set as possess gas phase catalysis agent feeding device 31 and the gaseous substance containing gas phase catalyst can be supplied in reaction vessel pipe 14, and possess halogen feedway 51, be configured in can react in reaction vessel pipe 14 containing iron group element material M and the halogen-containing material supplied from halogen feedway 51 in reaction vessel pipe 14.
The manufacture method of 2.CNT array
The manufacture method of the CNT array of an example of the present invention is illustrated.The manufacture method of the CNT array of this example possesses the first operation and the second operation.
(1) first operation
In the manufacture method of the CNT array of this example, as the first operation, the gas phase catalyst containing the material making the halogen-containing substance reaction gained containing iron group element material M and gas phase of solid phase is supplied in the first chamber.About the reaction containing the halogen-containing material of iron group element material M and gas phase of this solid phase, can carry out outside reaction vessel pipe 14 as using the situation of the manufacturing installation 10 of CNT array, also can carry out in reaction vessel pipe 14 as the situation of the manufacturing installation 50 or manufacturing installation 60 that use CNT array.Like this, the substrate 28 be configured in reaction vessel pipe 14 is present in the environment containing gas phase catalyst.
Here, in the manufacture method of the CNT array of this example, substrate 28 preferably possesses basal plane as its surface at least partially, and described basal plane is the face of the material of the oxide compound comprised containing silicon.
The concrete formation of substrate 28 indefinite.Its shape is arbitrarily, can be flat board or the such simple shape of cylinder, also can have the 3D shape being provided with complex unevenness on its.In addition, can make whole of substrate for basal plane, the only part that also can be the surface of substrate is for basal plane and other parts state that to be not the what is called of basal plane patterned.
Basal plane is the face of the material of the oxide compound comprised containing silicon, in the second operation, form CNT array on basal plane.As long as form the material of basal plane containing the oxide compound of silicon, then its details indefinite.The concrete example forming the material of basal plane can enumerate quartz (SiO
2).Other examples forming the material of basal plane can enumerate SiO
x(x≤2), this basal plane obtains by sputter silicon etc. under containing the environment of aerobic.And then other example can enumerate the composite oxides containing silicon.The element formed beyond the silicon of these composite oxides and oxygen can illustrate Fe, Ni, A1 etc.In addition, so other example can enumerate the compound being added with the non-metallic element such as nitrogen, boron in the oxide compound of silicon.
The material forming basal plane can be identical with the material forming substrate 28, also can be different.If illustrate concrete example, then can illustrate: form the material of substrate 28 and comprise quartz and the material that the material forming basal plane also wraps quartzous situation or forms substrate 28 comprises the silicon substrate using silicon as main body and the material being formed basal plane comprises the situation of its oxide film.
As described above, in the first operation, gas phase catalysis agent feeding device 31 is used in manufacturing installation 10, in manufacturing installation 50 or manufacturing installation 60, use halogen feedway 51 and be configured in reaction vessel pipe 14 containing iron group element material M, to supply gas phase catalyst in reaction vessel pipe 14, the substrate 28 possessing basal plane described in making is present in the environment containing gas phase catalyst.No matter using the manufacturing installation 10 of which kind of CNT array, manufacturing installation 50, manufacturing installation 60, all by suitably selecting containing the composition of iron group element material M and the kind of halogen-containing material, and various gas phase catalyst being supplied in reaction vessel pipe 14.
Containing the material that iron group element material M is containing iron family element ting (that is, at least one of iron, cobalt and nickel), it is composition also indefinite specifically.Concrete example containing iron group element material M can enumerate iron-based alloy (steel), cobalt base alloy, nickel-base alloy, and alloying element can illustrate other iron family element tings, chromium, manganese, titanium, niobium, vanadium, silicon, phosphorus, tungsten, molybdenum etc.Can be made up of a kind of material containing iron group element material M, also can be made up of multiple material.From the easy degree obtained, the viewpoint such as easy degree forming CNT, containing the iron family element ting contained by iron group element material M preferably containing iron.
Halogen-containing material is the material containing halogen (that is, at least one of fluorine, chlorine, bromine and iodine), and it is composition also indefinite specifically.The concrete example of halogen-containing material can enumerate hydrogen fluoride (HF), hydrogenchloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI) etc.Halogen-containing material can be made up of a kind of material, also can be made up of many kinds of substance.
The gas phase catalyst of this example contains the reaction product containing iron group element material M and halogen-containing material, and its concrete example can enumerate the halogenide (also referred to as " iron family element ting halogenide " in this specification sheets) of iron family element ting.If this iron family element ting halogenide of particular instantiation, then can enumerate ferric fluoride, cobaltous fluoride, nickelous fluoride, iron(ic) chloride, cobalt chloride, nickelous chloride, iron bromide, cobaltous bromide, nickelous bromide, ferric iodide, cobaltous iodide, nickelous iodide etc. further.Sometimes also as iron(ic) chloride (II), iron(ic) chloride (III), there is different compounds according to the valence mumber of the ion of iron family element ting in iron family element ting halogenide.Gas phase catalyst can be made up of a kind of material, also can be made up of many kinds of substance.
Except any one supply method described, additive method also can be used to the internal feed gas phase catalyst of reaction vessel pipe 14.If illustrate the concrete example of this situation, then can at the anhydride of the internal configuration iron(ic) chloride (II) of the heating region of reaction vessel pipe 14 as catalyst source, the inside of the heating region of reaction vessel pipe 14 one side heating one side is adjusted to negative pressure and the anhydride of iron(ic) chloride (II) is distilled, the gas phase catalyst of the steam containing iron(ic) chloride (II) is present in reaction vessel pipe 14.
Environment in reaction vessel pipe 14 in first operation, the pressure in growth region being configured with substrate 28 are specifically not particularly limited.Can be normal atmosphere (1.0 × 10
5about Pa), also can be negative pressure, also can be malleation.By when being set as subnormal ambient in reaction vessel pipe 14 in the second operation, preferably in the first operation, also environment is redefined for negative pressure, shortens the transit time of inter process.When in the first operation by when being set as subnormal ambient in reaction vessel pipe 14, the concrete stagnation pressure of environment is not particularly limited.If enumerate an example, then can enumerate and be set as 10
-2more than Pa and 10
4below Pa.
When using gas phase catalysis agent feeding device 31 to supply gas phase catalyst, the temperature of reaction vessel pipe 14 environment in the first operation is not particularly limited.Can be normal temperature (about 25C), also can through heating, also can through cooling.
As describing hereinafter, preferably in the second operation, the growth region of reaction vessel pipe 14 will be heated, therefore sometimes also preferably also this growth region will be heated in advance in the first operation, shorten the transit time of inter process.
When improving the temperature in growth region of reaction vessel pipe 14 in the first operation, if do not carry out special cooling, then the temperature being configured in the substrate 28 in growth region also improves.As a result, the environment composition depending on growth region is different, and in the first operation, the temperature of substrate 28 uprises and may impact forming catalyzer etc. on the basal plane of substrate 28 sometimes.This concrete example can be enumerated: when when be supplied to from gas phase catalysis agent feeding device 31 in the gaseous substance in reaction vessel pipe 14 containing halogen-containing material, such as hydrogen halide, can the catalyzer formation etc. forming this halogen-containing material on the basal plane of substrate 28 be impacted.When preferably reducing this and affecting, as long as unduly improve the temperature in the growth region of the reaction vessel pipe 14 in the first operation.That is, the temperature of the substrate 28 in the first operation also preferred temperature lower than the substrate 28 in the second operation sometimes.
When using halogen feedway 51 to supply gas phase catalyst, the temperature of reaction vessel pipe 14 environment must be improved until following degree, that is, halogen-containing material reacts with containing iron group element material M and generates a kind of material becoming gas phase catalyst in reaction vessel pipe 14.This temperature be kind according to halogen-containing material, containing the environment in the kind of iron group element material M, reaction vessel pipe 14 pressure etc. and set.Even if in this case, also when worrying to produce such problem mentioned above, the such formation of the manufacturing installation 60 of CNT array is preferably adopted unduly to improve to make the temperature of substrate 28.
In the first operation, when can supply the halogen-containing material beyond gas phase catalyst in reaction vessel pipe 14, following material is there is in this halogen-containing material, this material may play function as the etching reagent (etchant) being formed in the catalyzer on the basal plane of substrate 28 by enforcement first operation, thus the formation of CNT is impacted (as described above, the concrete example of this halogen-containing material can enumerate hydrogen halide).When preferably reducing this and affecting, as long as the halogen-containing material limited beyond this gas phase catalyst is to the feed rate in reaction vessel pipe 14, unduly improve with the concentration of the described halogen-containing material making (particularly in growth region) in reaction vessel pipe 14.
In addition, except described method, also the supply source of anhydride as gas phase catalyst of iron(ic) chloride (II) can be used, iron(ic) chloride (II) is distilled the heating of the anhydride of this iron(ic) chloride (II), the steam of produced iron(ic) chloride (II) is imported to and is configured with in the reaction vessel pipe 14 of substrate 28.The sublimation temperature of iron(ic) chloride (II) is at normal atmosphere (1.0 × 10
5about Pa) under be about 950K, but be set as negative pressure by the internal medium of the heating region by reaction vessel pipe 14, can sublimation temperature be reduced.
(2) second operations
In the second operation, use the catalyzer generated based on the gas phase catalyst existed in the first chamber, the carbon source contained by the unstripped gas be supplied in described first chamber is to form CNT.Specifically, using the gas phase catalyst containing the reaction product containing iron group element material M and halogen-containing material as catalyst precursors, substrate 28 generates catalyzer, uses this catalyzer by carbon source to form CNT.
The kind of unstripped gas is not particularly limited, and usually uses hydrocarbon system material, can enumerate acetylene as concrete example.The method making unstripped gas be present in (region of particularly growing up) in reaction vessel pipe 14 is not particularly limited.As manufacturing installation 10 mentioned above, manufacturing installation 50, manufacturing installation 60, by making unstripped gas exist from material gas supply device 30 base feed gas, also the material that can generate unstripped gas can be made to preexist in the inside of reaction vessel pipe 14, generate unstripped gas by this material and make it in the internal divergence of reaction vessel pipe 14, starting the second operation thus.When from material gas supply device 30 base feed gas, preferably use traffic adjustment equipment, controls the supply flow rate of the unstripped gas to reaction vessel pipe 14 inside.Usual supply flow rate is with sccm unit representation, and so-called 1sccm refers to and is converted into 273K, 1.01 × 10
5the flow of the per minute 1ml of the gas under the environment of Pa.When the manufacturing installation 10 of Fig. 1, Fig. 3, formation as shown in Figure 4, manufacturing installation 50, manufacturing installation 60, the flow being supplied to the gas in reaction vessel pipe 14 sets based on the pressure measured in the internal diameter of reaction vessel pipe 14, pressure warning unit 13 etc.Be 1 × 10 at the pressure of pressure warning unit 13
2more than Pa and 1 × 10
3when within Pa, the preferred supply flow rate of the unstripped gas containing acetylene can illustrate more than 10sccm and below 1000sccm, more preferably be set as more than 20sccm and below 500sccm in this situation, particularly preferably be and be set as more than 50sccm and below 300sccm.
In this specification sheets, so-called " gas phase catalysis auxiliary agent " refers to following gas phase composition, this gas phase composition has the function (hereinafter also referred to " growth promotion functions ") improved by the growth rate of the CNT array manufactured by gas-phase catalysis mentioned above, in a preferred form, there is the function (hereinafter also referred to " textile raising function ") of the textile of the CNT array manufactured by raising further.The details of growth promotion functions is not particularly limited.About the concrete composition of gas phase catalysis auxiliary agent, improve function as long as play described growth promotion functions and preferably play textile further, be then not particularly limited, a concrete example can enumerate acetone.
The method making gas phase catalysis auxiliary agent be present in (region of particularly growing up) in reaction vessel pipe 14 in the second operation is not particularly limited.Can, as manufacturing installation 10 mentioned above, manufacturing installation 50, manufacturing installation 60, by supplying gas phase catalysis auxiliary agent from gas phase catalysis auxiliary agent feedway 32, gas phase catalysis auxiliary agent be existed.When supplying gas phase catalysis auxiliary agent from gas phase catalysis auxiliary agent feedway 32, preferably use traffic adjustment equipment, controls the supply flow rate of the gas phase catalysis auxiliary agent to reaction vessel pipe 14 inside.Or, the material that can generate gas phase catalysis auxiliary agent also can be made to preexist in reaction vessel pipe 14, generate gas phase catalysis auxiliary agent by methods such as heating, decompressions by this material, make gas phase catalysis auxiliary agent at reaction vessel pipe 14 internal diffusion.
The stagnation pressure of reaction vessel pipe 14 environment in the second operation is not particularly limited.Can be normal atmosphere (1.0 × 10
5about Pa), also can be negative pressure, also can be malleation.As long as consider to be present in the composition (intrinsic standoff ratio) of material in reaction vessel pipe 14 etc. and suitably set.If illustrate the concrete example of the pressure range internal medium of the heating region in reaction vessel pipe 14 being set as the situation of negative pressure, be then 1 × 10
1more than Pa and 1 × 10
4below Pa, is preferably set as 2 × 10
1more than Pa and 5 × 10
3below Pa, is more preferably set as 5 × 10
1more than Pa and 2 × 10
3below Pa, particularly preferably is and is set as 1 × 10
2more than Pa and 1 × 10
3below Pa.
About the temperature in the growth region of the reaction vessel pipe 14 in the second operation, as long as under the condition that can be present in growth region with suitable amount at gas phase catalyst and the gas phase catalysis optionally used auxiliary agent, use unstripped gas on the basal plane of substrate 28, form CNT array, be then not particularly limited.As described above, sometimes the temperature on the basal plane of the substrate 28 in the first operation is set the low catalyzer also contributed on this basal plane is formed, in this case, the temperature in the growth region of the reaction vessel pipe 14 in the second operation is sometimes also changed to make it higher than the temperature in the growth region in the first operation.
The temperature of the basal plane in the second operation also controls by the temperature in the growth region of adjustment reaction vessel pipe 14.The temperature of the basal plane of the substrate 28 in the second operation is preferably heated to 8 × 10
2more than K.Be 8 × 10 in the temperature of the basal plane of substrate 28
2when more than K, gas phase catalyst and the gas phase catalysis auxiliary agent optionally used and unstripped gas easily produce and interact on basal plane, and CNT array is easily grown up on the basal plane of substrate 28.From more easily producing this interactional viewpoint, the temperature of the basal plane in the second operation is preferably heated to 9 × 10
2more than K, is more preferably heated to 1.0 × 10
3more than K, particularly preferably is and is heated to 1.1 × 10
3more than K.The upper limit of the temperature of the basal plane of the substrate 28 in the second operation is not particularly limited, but when excessively high, sometimes form the material of basal plane or form the material (these materials are also identical sometimes) of substrate and also lack stability as solid, therefore preferably considering the melting point of these materials or sublimation temperature and capping.If consider the load of reaction vessel pipe, then the ceiling temperature of substrate 28 is preferably set as 1.5 × 10
3about K.
3.CNT array
As shown in FIG. 5, possess with lower part by an example of the CNT array manufactured by the manufacture method of this example, this part has many CNT with the structure configured towards the mode of certain orientation orientation.If measure diameter to many CNT of this part and obtain the distribution of these diameters, then as shown in FIG. 6, the diameter of CNT becomes in the scope of 20nm ~ 50nm mostly.Electron microscope etc. can be utilized to observe the CNT forming CNT array, and measure the diameter of CNT according to the observation image of gained.
Textile should can be had by the CNT array manufactured by the manufacture method of this example.Specifically, by pinching the CNT forming CNT array, and extracting it out (weaving) towards the direction away from CNT array, the structure (CNT entwine body) possessing many CNT entwined each other can be obtained.Fig. 7 represents that forming CNT by CNT array entwines the image of state of body, and Fig. 8 is a part of enlarged image of body of being entwined by CNT.As shown in FIG. 7, the CNT forming CNT array extracted out continuously and form CNT and to entwine body.In addition, as shown in FIG. 8, direction (weaving direction) orientation that the CNT court that formation CNT entwines body extracts out from CNT array, and entwine each other and form interlocking matrix.In this specification sheets, will CNT array be possessed and the entwine component of body of CNT can be formed and be called " weaving source component ".
4.CNT entwines body
Different shape can be had by the CNT of weaving source component gained body of entwining.A concrete example can enumerate the shape of wire, and another example can enumerate netted shape.CNT about wire entwines body, if in order to obtain this CNT entwine body and weaving source component is extracted out time afterturn, then can operate comparably with fiber, and can be used as electrical wiring.In addition, netted CNT body of entwining can directly operate in the same manner as non-woven fabrics.
The entwine weaving direction length of body of CNT is not particularly limited, as long as suitably set according to purposes.If usually weaving length is more than 2mm, then can applies CNT to the part level such as contact part, electrode (level) and to entwine body.In addition, the CNT of wire body of entwining at random controls to form this CNT and to entwine the degree of orientation of CNT of body by changing the method (concrete example can enumerate the degree of afterturn) of to carry out weaving from weaving source component.Therefore, by changing the method for carrying out weaving from weaving source component, can manufacturing machine characteristic or the different CNT of electrical characteristic to entwine body.
If CNT entwines, body reduces its degree of entwining, then attenuate when wire, thinning when netted.If its degree improves, be then difficult to range estimation and confirm that CNT entwines body, now this CNT body of entwining can be used as vitreous fibre, transparent wiring, transparent network (transparent flat member).
CNT body of entwining only can comprise CNT, also can be the complex structure body with other materials.As described above, CNT body of entwining has the structure that many CNT entwine each other, therefore between these many CNT entwined, there is space in the same manner as the many fibers forming not duty cloth.By importing powder (the organic system particle such as the inorganic system particle such as metal microparticle, silicon-dioxide or ethylene-based polymer) or containing immersion fluid, easily can form complex structure body in this space part.
In addition, form CNT entwine the surface of CNT of body also can through upgrading.CNT due to outer side be made up of Graphene, therefore CNT body of entwining keeps hydrophobicity, but carries out hydrophilicity-imparting treatment by the surface of CNT of body of entwining to formation CNT, and CNT can be made to entwine body hydrophilization.One example of the method for this hydrophilization can enumerate plating.In this situation, the CNT of gained body of entwining becomes the complex structure body of CNT and metal lining.
5. there is manufacturing installation and the manufacture method of the CNT of the shape beyond array configuration
The manufacturing installation 10 of CNT array mentioned above, manufacturing installation 50, manufacturing installation 60 can be used, manufacture the CNT of the shape had beyond array configuration.Such as, can so that the end fixed state of each CNT be formed the aggregate that there is no anisotropy and bending CNT on substrate 28, the aggregate of this CNT of result is have to can be used as the CNT (in this specification sheets, being called " CNT net " by the aggregate of this CNT) that three dimensional network plays the secondary structure of function.CNT net is by with under type manufacture: in the method identical with the manufacture method of CNT array, namely the manufacturing installation 10 of CNT array mentioned above, manufacturing installation 50, manufacturing installation 60 is utilized to perform in the method for the first operation (supply of gas phase catalyst) and the second operation (supply of carbon source), adjustment manufacturing condition.CNT net can be used as having the component of the such function of the projection (bump) of flip-chip (flipchip).
In addition, also CNT can be manufactured with the form of the product of gas phase flowing reactive.Specifically, as long as under the state being configured with non-placement substrate in the growth region of substrate 28 when manufacturing CNT array, implement the first operation (supply of gas phase catalyst) and the second operation (supply of carbon source), the gas phase catalyst be then present in growth region produces chemical interaction with the unstripped gas containing carbon source, can form CNT in growth region with the form of the product of gas phase flowing reactive.Now, the degree that the CNT grown up in growth region is not easy can to have an array configuration with these CNT each other close to and grow up, therefore result can obtain the low CNT of shape anisotropy.
From the viewpoint more stably obtaining CNT with the form of the product of gas phase flowing reactive, also can supply gas phase catalyst before base feed gas.Namely, if the unstripped gas containing carbon source be supplied in reaction vessel pipe 14 and make carbon source be present in reaction vessel pipe 14, be supplied to by gas phase catalyst in reaction vessel pipe 14 in this condition, then the gas phase catalyst be supplied in reaction vessel pipe 14 can promptly interact with carbon source and form CNT.In this situation, the whole region that the unstripped gas in reaction vessel pipe 14 exists can become growth region.In addition, the region be supplied to by gas phase catalyst in reaction vessel pipe 14 can be included in growth region.From the viewpoint more stably obtaining CNT with the form of the product of gas phase flowing reactive, the set direction A of reaction vessel pipe 14 also can be vertical down.
Example described above records to easily understand the present invention, is not intended to limit the present invention and record.Therefore, each key element disclosed in described example is also comprise the purport belonging to all design alterations in technical scope of the present invention or equipollent.
Embodiment
Below, by embodiment etc., the present invention is more specifically illustrated, but scope of the present invention is not limited to these embodiments etc.
(embodiment 1)
Use the CNT array manufacturing installation with the structure shown in Fig. 4 to manufacture CNT array.Prepare 8g as the iron powder (325 orders, median size: 45 μm ~ 50 μm) containing iron group element material, this iron powder is positioned on the medial surface of the tubular member in the downstream side being arranged on halogen feedway in the first chamber.
Prepare quartz plate (20mm × 5mm × thick 1mm) as substrate.Therefore, in the present embodiment, the material forming basal plane and the material forming substrate are quartz.Be positioned at the part in downstream side of reaction vessel pipe, to be positioned in the state configuration quartz plate in the quartzous boat of bag.
Gas barrier is used to be vented to 1 × 10 by reaction vessel pipe
-1below Pa.Then, use well heater that the region of the upstream side of reaction vessel pipe is heated to 1.1 × 10
3k, is set as 1.1 × 10 by the temperature of the tubular member of the halogen feedway in reaction vessel pipe and mounting iron plate therein
3about K.In addition, the region in the downstream side of reaction vessel pipe is heated to 6.0 × 10
2k, is set as 6.0 × 10 by the temperature of quartz plate
2about K.
In this condition, from halogen feedway to supply HCl the amount becoming the flow of 5sccm, this HCl is supplied maintenance 20 minutes.Within this period, by the heating temperatures in the region in the downstream side of reaction vessel pipe to 8.0 × 10
2k, the temperature of the quartz plate from HCl supply through 20 minutes time becomes 8.0 × 10
2about K.Complete the first operation like this.
Then, stop, from halogen feedway supply HCl, under the state stopping HCl supply, spending 12 minutes by the heating temperatures in the region in the downstream side of reaction vessel pipe to 1.1 × 10
3k, is set as 1.1 × 10 by the temperature of quartz plate
3about K.
Then, 1.1 × 10 are set as in the temperature in the whole region by reaction vessel pipe
3under the state of K, from material gas supply device in reaction vessel pipe to become the acetylene 10 minute of amount supply as unstripped gas of the flow of 1000sccm, and from gas phase catalysis auxiliary agent feedway in reaction vessel pipe to become the amount supply of the flow of 50sccm as the acetone 10 minutes of gas phase catalysis auxiliary agent, implement the second operation thus.
As a result, as shown in FIG. 9, quartz plate obtains CNT net.
Use laman spectrophotometer (" NR-1800 " that Japanese light splitting company manufactures), measure Raman spectrum to the CNT net of gained, calculate G/D ratio, its value of result is 2.92.
(embodiment 2)
In embodiment 1, the feed rate of HCl is set as the amount becoming 10sccm, in addition, carries out the operation identical with embodiment 1, implement the first operation and the second operation.
As a result, as shown in FIG. 10, quartz plate obtains CNT net.The G/D ratio forming the CNT of the CNT net of gained is 2.49.
(embodiment 3)
In embodiment 1, the feed rate of HCl is set as the amount becoming 15sccm, in addition, carries out the operation identical with embodiment 1, implement the first operation and the second operation.
As a result, as shown in Figure 11, quartz plate obtains CNT array.The G/D ratio forming the CNT of the CNT array of gained is 2.19.
(embodiment 4)
In embodiment 1, the feed rate of HCl is set as the amount becoming 20sccm, in addition, carries out the operation identical with embodiment 1, implement the first operation and the second operation.
As a result, as shown in Figure 12, quartz plate obtains CNT array.The G/D ratio forming the CNT of the CNT array of gained is 2.53.
(embodiment 5)
In embodiment 1, the feed rate of HCl is set as the amount becoming 25sccm, in addition, carries out the operation identical with embodiment 1, implement the first operation and the second operation.
As a result, as shown in Figure 13, quartz plate obtains CNT array.The G/D ratio forming the CNT of the CNT array of gained is 1.81.
(embodiment 6)
In embodiment 1, the feed rate of HCl is set as the amount becoming 30sccm, in addition, carries out the operation identical with embodiment 1, implement the first operation and the second operation.
As a result, as shown in Figure 14, quartz plate obtains CNT net.The G/D ratio forming the CNT of the CNT net of gained is 2.58.
(embodiment 7 ~ embodiment 12)
Substrate is adjusted to the silicon substrate with heat oxide film by quartz plate, changes to by the quartzous basal plane of bag the basal plane comprising silicon oxide layer, in addition, carry out the operation identical with embodiment 1 ~ embodiment 6.By the result of these embodiments and G/D than with the results are shown in table 1 of embodiment 1 ~ embodiment 6.
[table 1]
(embodiment 13 ~ embodiment 16)
Use the ferric oxide (Fe russet of 1.0g
2o
3) powder (100 orders, median size: 140 μm ~ 150 μm) replace iron powder as containing iron group element material, and the feed that occupies of the HCl from halogen feedway is set as 2.5sccm (embodiment 13), 5sccm (embodiment 14), 7.5sccm (embodiment 15) and 10sccm (embodiment 16), in addition, carry out the operation identical with embodiment 1, implement the first operation and the second operation.As a result, CNT array (with reference to Figure 15) is all obtained in arbitrary situation.In addition, in arbitrary situation, the iron group element material that contains remained in after the second operation on the medial surface of annular component is black.
[industrial utilizability]
The CNT of the CNT array gained manufactured by the manufacture method by CNT of the present invention entwines style as being used as electrical wiring, heating element, deformation-sensor, transparent electrical pole piece etc. suitably.In addition, the electrode materials of secondary cell can be used as suitably by the CNT net manufactured by the manufacture method of CNT of the present invention or the CNT without specific secondary structure.
[explanation of symbol]
10,50, the manufacturing installation of 60:CNT array
12: electric furnace
13: pressure warning unit
14: reaction vessel pipe (the first chamber)
16: well heater (part for the first register)
18: thermopair (part for the first register)
20: control device
22: feedway
23: relief valve (part for regulator)
24: gas barrier (part for regulator)
28: substrate
30: material gas supply device (the first feedway)
31: gas phase catalysis agent feeding device
32: gas phase catalysis auxiliary agent feedway
33: assist gas feedway
31A: feed unit chamber
31B: well heater (part for the second register)
31C: halogen-containing material feeding device (the second feedway)
31D: releasing device
51: halogen feedway
61: tubular member
Claims (16)
1. a manufacturing installation, manufactures carbon nanotube by gas-phase catalysis, and the feature of described manufacturing installation is to possess:
First chamber, has the growth region as the region forming carbon nanotube;
First register, the temperature in the described growth region in the first chamber described in adjustable;
Regulator, the pressure in the first chamber described in adjustable;
First feedway, can to the described growth region supply carbon source in described first chamber;
Second register, adjustable is configured in the temperature containing iron group element material of the solid phase in described manufacturing installation; And
Second feedway, can supply halogen-containing material in described manufacturing installation, with make through described second register be adjusted to described in determined temperature containing iron group element material can with the described halogen-containing substance reaction of gas phase.
2. manufacturing installation according to claim 1, is wherein configured with substrate in described growth region, can form carbon nanotube on the basal plane of described substrate with array-like.
3. manufacturing installation according to claim 1, wherein in described growth region, forms carbon nanotube by gas phase flowing reactive.
4. manufacturing installation according to any one of claim 1 to 3, possesses and can accommodate described iron content race element material and its inner second chamber be communicated with the inside of described first chamber, and
Described second feedway can supply described halogen-containing material in described second chamber.
5. manufacturing installation according to any one of claim 1 to 3, possesses the second chamber can accommodating described iron content race element material and the 3rd feedway that the gaseous substance be present in described second chamber can be supplied in described first chamber, and
Described halogen-containing material can be supplied in described second chamber by described second feedway.
6. manufacturing installation according to any one of claim 1 to 3, is wherein configured in described in described first chamber containing iron group element material.
7. a feed unit, it is the feed unit of gas phase catalyst, and becomes a part for the manufacturing installation being manufactured carbon nanotube by gas-phase catalysis, and the feature of described feed unit is to possess:
Feed unit chamber, that can accommodate solid phase contains iron group element material;
Feed unit register, containing the temperature of iron group element material described in feed unit chamber described in adjustable;
Halogen-containing material feeding device, can supply halogen-containing material in described feed unit chamber; And
Releasing device, can be released to the described gas phase catalyst be present in described feed unit chamber outside described feed unit chamber.
8. a manufacture method for carbon nanotube, uses feed unit according to claim 7, and the basal plane of substrate obtains the carbon nanotube formed with array-like.
9. a manufacture method for carbon nanotube, uses feed unit according to claim 7, obtains carbon nanotube with the form of the product of gas phase flowing reactive.
10. a manufacture method, manufacture carbon nanotube, and the feature of described manufacture method is to possess:
First operation, is supplied in the first chamber by the gas phase catalyst containing the material making the halogen-containing substance reaction gained containing iron group element material and gas phase of solid phase; And
Second operation, uses the catalyzer generated based on the gas phase catalyst existed in described first chamber, by the carbon source be supplied in described first chamber to form carbon nanotube.
11. manufacture method according to claim 10, wherein in described first operation, make the substrate be configured in described first chamber be present in the environment containing described gas phase catalyst,
In described second operation, the basal plane of described substrate forms carbon nanotube with array-like.
12. manufacture method according to claim 11, wherein under the state that described gas phase catalyst is present in the first chamber through described first operation, supply described carbon source in described first chamber.
13. manufacture method according to claim 11 or 12, the temperature of the described substrate in wherein said first operation is lower than the temperature of the described substrate in described second operation.
14. manufacture method according to claim 10, wherein form carbon nanotube with the form of the product of gas phase flowing reactive.
15. according to claim 10 to the manufacture method according to any one of 14, and the wherein said iron family element ting contained contained by iron group element material comprises iron.
16. according to claim 10 to the manufacture method according to any one of 15, wherein in described first operation, outside described first chamber, carry out the reaction obtaining described gas phase catalyst, described gas phase catalyst is supplied in described first chamber from described first chamber.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-177237 | 2013-08-28 | ||
| JP2013177237 | 2013-08-28 | ||
| PCT/JP2014/072623 WO2015030132A1 (en) | 2013-08-28 | 2014-08-28 | Production device for carbon nanotubes and supply unit to become one part of said production device, and production method for carbon nanotubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105492383A true CN105492383A (en) | 2016-04-13 |
| CN105492383B CN105492383B (en) | 2017-06-23 |
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| CN201480046650.8A Expired - Fee Related CN105492383B (en) | 2013-08-28 | 2014-08-28 | The manufacture method of manufacture device, feed unit and CNT |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US20160207772A1 (en) |
| JP (1) | JP5942069B2 (en) |
| CN (1) | CN105492383B (en) |
| WO (1) | WO2015030132A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389401A (en) * | 2006-02-24 | 2009-03-18 | 大阳日酸株式会社 | Catalyst for carbon nanostructure growth, process for producing carbon nanostructure, raw-material gas and carrier gas for producing the same, and apparatus for producing the same |
| WO2009107603A1 (en) * | 2008-02-25 | 2009-09-03 | 国立大学法人静岡大学 | Process and apparatus for producing carbon nanotube, carbon nanotube fiber, and the like |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4392991A (en) * | 1981-09-21 | 1983-07-12 | Westinghouse Electric Corp. | Method of making α-hematite catalyst |
| GB0201600D0 (en) * | 2002-01-24 | 2002-03-13 | Univ Cambridge Tech | Large- scale plasma synthesis of hollow nanostructures |
| EP1560791A1 (en) * | 2002-11-15 | 2005-08-10 | MGill University | Method for producing carbon nanotubes using a dc non-transferred thermal plasma torch |
| US20050112050A1 (en) * | 2003-11-21 | 2005-05-26 | Pradhan Bhabendra K. | Process to reduce the pre-reduction step for catalysts for nanocarbon synthesis |
| KR20080113269A (en) * | 2006-03-29 | 2008-12-29 | 하이페리온 커탤리시스 인터내셔널 인코포레이티드 | Method for preparing uniform single walled carbon nanotubes |
| US7601294B2 (en) * | 2006-05-02 | 2009-10-13 | Babcock & Wilcox Technical Services Y-12, Llc | High volume production of nanostructured materials |
-
2014
- 2014-08-28 WO PCT/JP2014/072623 patent/WO2015030132A1/en active Application Filing
- 2014-08-28 US US14/914,625 patent/US20160207772A1/en not_active Abandoned
- 2014-08-28 CN CN201480046650.8A patent/CN105492383B/en not_active Expired - Fee Related
- 2014-08-28 JP JP2015534294A patent/JP5942069B2/en not_active Expired - Fee Related
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2017
- 2017-12-11 US US15/836,920 patent/US10464814B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389401A (en) * | 2006-02-24 | 2009-03-18 | 大阳日酸株式会社 | Catalyst for carbon nanostructure growth, process for producing carbon nanostructure, raw-material gas and carrier gas for producing the same, and apparatus for producing the same |
| WO2009107603A1 (en) * | 2008-02-25 | 2009-09-03 | 国立大学法人静岡大学 | Process and apparatus for producing carbon nanotube, carbon nanotube fiber, and the like |
Non-Patent Citations (1)
| Title |
|---|
| HAOQING HOU ET AL.: "Large-Scale Synthesis of Aligned Carbon Nanotubes Using FeCl3 as Floating Catalyst Precursor", 《CHEM. MATER》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180105424A1 (en) | 2018-04-19 |
| US20160207772A1 (en) | 2016-07-21 |
| WO2015030132A1 (en) | 2015-03-05 |
| JPWO2015030132A1 (en) | 2017-03-02 |
| JP5942069B2 (en) | 2016-06-29 |
| CN105492383B (en) | 2017-06-23 |
| US10464814B2 (en) | 2019-11-05 |
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